Water-insoluble mono- and disazo-dyes produced from 2-aminoaryl-benztriazole-1-oxide diazo components



United States Patent 3,099,651 WATER-INSOLUBLE MONO- AND DISAZO-DYES PRODUCED FROM Z-AMHNOARYL-BENZTRIA- ZOLE-l-OXIDE DIAZO COMPONENTS Richard Gross, Frankfurt am Main, and Hasso Hertel, Werner Kirst, and Reinhard Mohr, Offenbach (Main), Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Briining, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed May 17, 1960, Ser. No. 29,577 Claims priority, application Germany May 20, 1959 6 Claims. (Cl. 260-1l46) The present invention relates to new water-insoluble azo-dyestuffs containing metal and to a process for preparing them; more particularly it relates to water-insoluble azo-dyestuffs containing metal which, when free from metal, correspond to the following general formula wherein A and B represent radicals of the benzene or naphthalene series and R represents the radical of an arylamide of an aromatic or heterocyclic ortho-hydroxycarboxylic acid or an acylacetic acid.

We have found that new water-insoluble azo-dyestufls containing metal are obtained by coupling in substance, on the fiber or on another substratum the diazonium compounds of amines corresponding to the general formula wherein A and B represent radicals of the benzene or naphthalene series, with arylamides of aromatic or heterocyclic ortho-hydroxycarhoxylic acids or acylacetic acids, the diazo and coupling components containing no groups imparting solubility in water such, for example, as sulfonic acid or carboxylic acid groups, and treating the dyestuffs thus obtained with agents yielding metal.

The treatment of the water-insoluble azo-dyestufis obtainable according to the process of this invention with the agents yielding metal may be carried out by known methods during or after the coupling in substance or on the fiber. When the dyestuffs are produced on the fiber, the motallisation may be effected by adding the agents yielding metal to the developing bath or by adding these compounds already to the impregnation bath. The treatment of the dyestuifs with agents yielding metal after the coupling may be carried out in a second bath which is neutral, weakly alkaline or Weakly acid and contains, if desired, dispersing agents and detergents, such as for example fatty alcohol polyglycolether, alkylphenol-polyglycolether, alkylnaphthol-polyglycolether, fatty acid polyglycolester or fatty acid amide polyglycolether.

As agents yielding metal, there may be preferably used for the process of the present invention agents yielding copper, cobalt and nickel which may be applied in the form of their inorganic or organic salts such as, for example, chlorides, bromides, sulfates, nitrates, formates or acetates, or as complex compounds, in particular with hydroxy-alkylamines, such for example as triethanolamine, with amino acids such as amino acetic acid or ice nitrilotriacetic acid, with hydroxy-carboxylic acids, such as citric acid or tartaric acid, or with alkali metal phosphates, such for example, as allcali-pyrophosphates or alkali-polyphosphates. When there is used an agent yielding cobalt, the addition of compounds of hexavalent chromium or other oxidizing agents, for example alkali metal perborates or alkali metal persulfates, proves to be favorable for the metallisartion. On vegetable fibers, including fibers of regenerated cellulose, there are obtained by dyeing and printing methods known from the ice color industry dyestuffs which, besides good general properties of fastness, possess a very good fastness to light. The brown tints obtainable with the use of arylamides of 2,3- hydroxy-naphthoic acid as coupling components and copper compounds as agents yielding metal are of particular value.

On vegetable fibers the dyestuffs may be prepared in long goods-to-liquor ratios. Piece goods, warps or bands may furthermore be dyed in a continuous manner, or by the base or naphtholate printing process.

The new dyestuffs may also be prepared on animal fibers such as wool or silk, as well as on synthetic fibers such as polyamide, acetyl-cellulose, or polyvinyl-alcohol fibers by the dyeing processes which are usual for these fibers whereby there are also obtained valuable dyeings possessing good properties of fastness.

The dyestuifs may also be prepared in substance and converted into complex metal compounds by a treatment with agents yielding metal. The metallisation may be etfected in an aqueous suspension, it is suitable, however, to eifect the metallisation in organic solvents, such for example, as acetone or dimethylformamide. The complex metal com-pounds thus obtained are suitable for dyeing animal and synthetic fibers as well as for coloring organic plastic masses of high molecular weight.

As coupling components for the process of the present invention, there may be used arylamides of aromatic or heterocyclic ortho-hydroxy-car-boxylic acids or acylacetic acids, such as the arylamides of 2,3-hydroxy-naphthoic acid or its derivatives substituted in 6-position, furthermore the arylamides of 2-hydroxy-anthracene-3-carboxylic acid, 3-hydroxy-dipl1enylene oxide-Z-carboxylic acid, 2-hydroxy-carbazole-3-carboxylic acid, 5-hydroxy-1,2,1, 2'-benzocarbazole-4-carboxylic acid, acetoacetic acid, benzoylacetic acid or terephthaloyl-bis-acetic acid.

As amino compounds which correspond to the above formula and may advantageously be used for the process of the present invention, there may be used compounds wherein the benzene or naphthalene radicals A and B may be substituted by groups which do not impart solubility in water such as halogen atoms, alkyl, alkoxy, aryloxy, arylamino, trifluoromethyl, sulfonic acid amide, or carboxylic acid amide groups. These amino compounds may be prepared according to the process described in US. patent application Serial No. 13,710 filed March 9, 1960 (now abandoned), and German Auslegeschrift 1,088,060.

The following examples serve to illustrate the invention but they are not intended to limit it thereto; the parts being by Weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter.

Example 1 Cotton yarn is treated for 45 minutes at 35 C. in a goods-to-liquor ratio of 1:20 in the following impregnation bath, centrifuged and, while being Wet, developed, first for some minutes at 20 C. and then, after being slowly heated to C. to 95 -C., for 20 to 30 minutes at C. to C. in the developing bath described below. The yarn is then rinsed with a solution containing per liter of water 3 cc. of hydrochloric acid of 20 B., soaped first for minutes at 60 C., then for 15 minutes at 95 C. With a solution containing per liter of water 1 gram of a reaction product from about 10 moles of ethylene oxide and 1 mol of isododecyl phenol, and furthermore 3 grams of sodium carbonate, rinsed and dried.

Impregnatzon bath-1.75 grams of 2(2,3-hydroxynaphthoylamino) -napththalene are dissolved in 3.5 cc. of denatured ethyl alcohol, 0.9 cc. of sodium hydroxide'solution of 38 B., 2 cc. of hot water and 0.9 cc. of a formaldehyde solution of 33% strength. The solution thus obtained is then made up to 1 liter with Water of 35 C., 3 grams of a condensation product from fatty acids of high molecular weight and protein degnadation products, and 10 cc. of a sodium hydroxide solution of 38 B.

Developing b'ath.-3.1 grams of 2-(2'-amino:-4',5-diethoxyphenyl)-benztriazole-1-oxide in the form of a dicompound prepared in the usual manner, are dissolved in 1 liter of water containing 2 grams of a reaction product firom about mols of ethylene oxide and 1 mol of octadecyl alcohol, 3 cc. of acetic acid of 50% strength, 10 grams of sodium acetate and 2.5 grams of copper sulfate.

A dark brown dyeing of a very good fastness to light is obtained. 7

When in the above example 2.4 grams of cobaltorus chloride or 2.8 grams of nickel sulfate are used instead of 2.5 grams of copper sulfate, a reddish brown, dyeing is obtained.

Example 2 Cotton fabric is treated for 45 minutes at 35 C. on the jig ina goods-to-liquor ratio of 1:5 in the following impregnation bath, rinsed for 5 minutes with a solution containing per liter of water 40 grams of sodium chlo ride and 0.5 cc. of sodium hydroxide solution of 38 B., and then developed for minutes at 18 C. to 20 C. in the developing bath described below. The fabric is then soaped for 15 minutes at 60 C. with a solution containing per liter of water 1 gram of a reaction product of about 10 mols of ethylene oxide and 1 mol of isododecyl phenol and 3 grams of sodium carbonate, then aftertreated for 15 minutes at 95 C. with a solution containing per liter of water 3.75 grams of copper sulfate, 9 cc. of triethanolann'ne, 1 gram of a reaction product from about 10 mols of ethylene oxide and 1 mol of isododecyl phenol, and furthermore 1 gram of sodium carbonate, rinsed again and dried.

Impregnation bath-4.2 grams of 2-(2',3'-hydroxynaphtholylamino)-napmthalene are dissolved in 8.5 cc. of denatured ethyl alcohol, 2.1 cc. of sodium hydroxide solution of 38 B., 5 cc. of hot water and 2.1 cc. of: a formaldehyde solution of 33% strength. The solution thus obtained is made up to 1 liter with water of 35 C., 3 grams of a condensation product of fatty acids of high molecular weight and protein degradation products and 10 cc. of sodium hydroxide solution of 38 B.

Developing bath.4.7 grams of 2-(2'-amino-4acetylamino 5' methylphenyl) 6 methyl beuztriazolel oxide, in the form of a diazonium compound prepared in the usual manner are dissolved in 1 liter of water containing 2 grams of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol, 3 cc. of acetic acid and 50% strength and 10 grams of sodium acetate.

A dark brown dyeing of an excellent fastness to light is obtained.

Example 3 Cotton fabric is padded on the foulard with the following solution and dried:

6.4 grams of 2,3-hydroxynapththoylaminobenzene are dissolved with 20 grams of Monopol Brilliant Oil and 15 cc. of sodium hydroxide solution of 38 B. and made up to 1 liter with boiling water.

The dried fabric is developed on the foulard with a solution containing per liter of water 9 grams of 2(2- amino 4 methoxy 5' methyl phenyl) benztriazole-iboxide in the form of a diazonium compound prepared in the usual manner, 2 grams of a reaction prodnot from about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol, and 10 cc. of acetic acid of 50% strength. After passage of air for 30 seconds the fabric is after-treated for 20 seconds at 98 C. with a solution containing per liter of Water 2.5 grams of copper sulfate and 6 grams of triethanolamine. The material is then rinsed hot and cold, soaped with a solution containing per liter of water 1 gram of a reaction product from about 10 mols of ethylene oxide and 1 mol of isododecylphenol, and 3 grams of sodium carbonate, rinsed and dried.

A reddish brown dyeing of good fastness to light is obtained.

Example 4 Cotton fabric is padded 0n the foulard with the following solutionand dried:

6.4 grams of 2,3-l1ydroxynapththoylaminobenzene are dissolved with 20 grams of Monopol Brilliant Oil and 15 cc. of sodium hydroxide solution of 38 B. and made up to 1 liter with boiling water. The dried fabric is developed on the foulard with a solution containing per liter of water 9 grams of 2-(2'-amino-4'-methoxy-5'- methyl-phenyl) benztriazole-hoxide in the form of a diazoni-um compound prepared in the usual manner, 2 grams of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadecyl-alcohol and 10 cc. of acetic acid of 50% strength. After passage of air for 30 seconds and a hot 'water passage, the material is soaped for 5 minutes at 60 C. with a solution containing per liter of water 5 grams of soap, rinsed and dried. The dried fabric is then printed with a printing paste containing per kilogram 200 grams of sodium-formaldelhyde-sulfoxyl-ate, 25 grams of the sodium salt of benzylsulfianilic acid, 50 grams of potassium carbonate, 30 grams. of an anthraquinone paste of 30% strength and starch-tragacanth as thickening agent. The material is then steamed for 7 minutes at 102 C. to 103 C., washed with hot dilute sodium carbonate solution, rinsed and after-treated for 15 minutes at C. to C. with a solution containing per liter of Water 1 gram of a reaction product from about 10 mols of ethylene oxide and 1 mol of isododecyl phenol, -1 gram of sodium carbonate, 3 grams of triethanolamine and 1.25 grams of copper sulfate. The material is then rinsed and dried.

A White discharge on brown base is obtained.

When vat dyestuffs are used in the printing paste, there may be prepared colour discharges on brown base.

Example 5 W001 yarn is treated for 45 minutes at 55 goods-to liquor ratio of 1:30 tion bath and rinsed for 5 minutes at 18 C. to 20 C. with a solution containing per liter of Water 40 grams of sodium chloride and 3 grams of sodium carbonate. The material is then allowed to drop off and treated first for 20 to 30 minutes at 18 C. and then for a further 20 to 30 minutes at 90 C. to 95 C. in the developing bath. The yarn is first soaped for 20 minutes at 40 C. with a solution containing per liter of Water 1 gram of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol, and furthermore 1 cc. of ammonia of 25% strength, and then tor 20 minutes at 85 C. with a solution containing per liter of water 1 gram of a condensation product from fatty acids of high molecular weight and an arninoalkylsulfonic acid, as well 138 0.5 cc. of acetic acid of 50% strength, rinsed and dried.

Impregnation bath.-1 (grain of 1-(2',3- hydroxynaphthoylamino)-2- methyl-4-chlorobenzene and 0.2 gram of C. in a 1n the following impregnasodium hydroxide are dissolved in 5 cc. of denatured ethyl alcohol, 4 cc. of Water of 60 C., 0.5 gram of a condensation product from fatty acids of high molecular weight and protein degradation products, and 1.2 cc. of a formaldehyde solution of 33% strength. The solution so obtained is made up to 1 liter with water of 60 C., 2.5 grams of a condensation product from fatty acids of high molecular weight and protein degradation products, and furthermore 3 grams of sodium carbonate.

Developing bath.-1.2 grams of 2-(2-amino-4',5-di ethoxyphenyl)-6-chloro-benztriazole-l-oxide in the "form of a diazonium compound prepared in the usual manner are dissolved in 1 liter of water containing 2 grams of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadecyl alcohol, 2 cc. of acetic acid of 50% strength, grams or sodium acetate and 1.8 grams of copper sulfiate.

A yellowish brown dyeing of good properties of fastness is obtained.

When in the above example 2.1 grams of nickel sulfate are used instead of 1.8 grams of copper sulfate, a reddish browu dyeing is obtained.

Example 6 Polyamide yarn is treated for 1 hour at 80 C. in a goods-to-liquor ratio of 1:20 in a solution containing per liter of water 1 gram of 1-(2,3'-hydroxynaphthoylamino)-2-methoxybenzene, 0.5 cc. of sodium hydroxide solution of 38 B., 10 cc. of denatured ethyl alcohol, 2 grams of Monopol Brilliant Oil and 0.7 gramof 2- (2 amino 4,5' di ethoxyphenyl) 6 methylbenztriazole-l-ox-ide. The yarn is then rinsed and treated for 30 minutes at 20 C. in a solution containing per liter of water 2 grams of sodium nitrite and 3 cc. of hydrochloric acid of 20 B. The material is then treated for 10 minutes at 60 C. with a solution containing per liter of Water 0.5 cc. of concentrated ammonia and 4 grams of sodium acetate, rinsed and metallized for 30 minutes at 90 C. to 95 C. with a solution containing per liter of water 2.5 grams of copper sulfate. The material is then rinsed, soraped for minutes at 90 C. with a solution containing per liter of water 1 gram of a reaction product from about 10 mols of ethylene oxide and 1 mol of isododecylphenol, and [furthermore 3 grams of sodium carbonate, rinsed and dried.

A full reddish brown dyeing of good properties of fastness is obtained.

When in the above example 2.4 grams of cobaltous chloride or 2.8 grams of nickel sulfate are used instead of 2.5 grams of copper sulfate, a reddish brown dyeing is obtained.

Example 7 Polyvinyl alcohol yarn is treated for 1 hour at 90 C. to 95 C. in a goods-to-liquor ratio of 1:30 in the following solution:

1 gram of 2,3-hydroxynaphthoylaminobenzene and 0.7 gram of 2-(2-amino-4',5-diethoxyphenyl)-6-methylbenztriaZole-l-oxide are dissolved in the hot with 0.5 cc. of sodium hydroxide solution of 38 B., 5 cc. of denatured ethyl alcohol, 5 cc. of dimethyl iorrnamide and 1 cc. of water, and the solution obtained is int-roduced into a bath containing per liter of Water 2 grams of Monopol Brilliant Oil (and 5 cc. of sodium hydroxide solution of 38 C. The material is then rinsed and treated for 30 minutes at 65 C. in a solution containing per liter of Water 2 grams of sodium nitrite and 3 cc. of hydrochloric acid of B. It is then rinsed, treated for 15 minutes at 30 C. to 35 C. with a solution containing per liter of water 4 grams of sodium acetate and 1 gram of a reaction product from about 10 mols of ethylene oxide and 1 mol of isododecylphenol, rinsed again, and metallized for 30 minutes at 90 C. with a solution containing per liter of water 2.5 grams of copper sulfate. The material is then soaped for 15 minutes at 60 C. with a solution containing per liter of water 1 gram of a reaction product from about 10 mols of ethylene oxide and 1 mol of isododecylphenol, and 3 grams of sodium carbonate, rinsed and dried.

A brown dyeing of good properties of fastness is obtained.

When in the above example 2.4 grams of cobaltous chloride or 2.8 grams of nickel sulfate are used instead of 2.5 grams of copper sulfate, a reddish brown dyeing is obtained.

Example 8 Natural silk is treated for 45 minutes at 25 C. in a goods-todiquor ratio of 1:30 in the following impregnation bath, centrifuged and, While being wet, developed first for 10 minutes at 25 C. and then, after being slowly heated to C. to C., for 15 to 30 minutes at this temperature in the developing bath described below. It is then rinsed, acidified with a solution containing per liter of water 3 cc. of hydrochloric acid of 20 B., soaped for 15 minutes at 95 C. with a solution containing per liter of water 5 grams of soap, rinsed and dried.

Impregnation bath.--3 grams of 2,3-hydroxynaphthoylaminobenzene are dissolved in 6 cc. of denatured ethyl alcohol, 1.5 cc. of sodium hydroxide solution of 38 B., 3 cc. of hot Water and 1.5 cc. of la dormaldehyde solution of 33% strength. This solution is made up to 1 liter with Water of 25 C., 5 grams of a condensation product from fatty acids of high molecular weight and protein degradation products, 4 cc. of sodium hydroxide solution of 38 B. and 10 grams of sodium chloride.

Developing bath.2.7 :grams of 2a(2'-amino-4'methoxy-5'-methylphenyl)-6-chloro-benztriazole 1 oxide in the form of a diazonium compound prepared in the usual manner are dissolved in 1 liter of water containing 2 grams of a reaction product from about 20 mols of ethylene oxide and 1 mol of octadccyl alcohol, 3 cc. of acetic acid of 50% strength, 10 grams of sodium acetate and 1.75 grams of copper sulfate.

A dark brown dyeing of very good iastness to light is obtained.

When in the above example 2 grams of nickel sulfate are used instead of 1.75 grams of copper sulfate and (the process is otherwise carried out in the manner described above, a dark brown dyeing of 'very good fastness to light is obtained.

Example 9 13.5 pants of 2-(2' amino 5' methyl 4' meth'oxyphenyl) benztriazoled oxide are stir-red with 50 parts by volume of Water and 40 parts by volume of hydrochloric acid density 1.16). After the addition of ice, the Whole is diazotized with 10 parts by volume of 5 N-sodium nitrite solution. The diazo-solution thus obtained is combined at 50 C. with a suspension of 2,3-hydroxynaphthoylaminobenzene prepared as follows:

13.15 parts of 2,3hydroxynaphthoylaminobenzene are dissolved in 20 parts by volume of denatured alcohol and 20 parts by volume of sodium hydroxide solution (density 1.19), diluted with parts by volume or water and introduced into a mixture of 1,000 parts by volume of water, 20 parts by volume of acetic acid and 1 part of a reaction product [from about 20 mols of ethylene oxide and 1 mol of oleyl alcohol. There is then added a solution of 81.6 parts of sodium acetate in 300 parts by volume of Water. Alter completion of the coupling, the 'whole is neutralized with sodium hydroxide solution, and a solution of 12.5 parts of copper sulfate and 45 parts of triethanolamine in 200 parts by volume of water is added thereto. The whole is then heated to 95 C. and treated ator 2 hours at this temperature. The dyestuflf formed is suction-filtered, washed and dried. It is a dark powder.

The following table indicates a number of further comwherein A and B represent members selected from the group consisting of radicals of the benzene and naphthalene series, R represents the radical of an arylamide selected from the group consisting of arylamides of the benzene, napthalene, diphenyl :and diphenylene oxide series, of an ortho-hydroxycarboxylic acid selected from the group consisting of 2,3-hydroxynaphthoic acid, 2,3- hydroxynaphthoic acid substituted in 6-position by a bromine atom, 2-hydroxy-anthracene-3-carboxylic acid, 3- hydroxy-diphenylene oxide-2-carboxylic acid, Z-hydroxycarbazole-3 -carboxylic acid and 5-hydroxy-l,2,l',2 '-benzocarbazole-4-carboxylic acid, and n stands for one of the integers l and 2.

2. The complex copper compound of the water-insoluble azo-dyestuif corresponding to the following formula:

II N 4. The complex copper compound of the Water-insoluble azo-dyestuif corresponding to the following formula:

5. The complex copper compound of the water-insoluble azo-dyest-uif corresponding to the following formula:

6. The complex copper compound of the water-insolu- 5 ble aZo-dyestuif corresponding to the following formula:

N-Q-OCQHE 4O CHaO- I N N g T -o 0-NH-@ References Cited in the file of this patent UNITED STATES PATENTS 2,212,816 Schultis et a1 Aug. 27, 1940 

1. A COMPLEX METAL COMPOUND CONTAINING A METAL SELECTED FROM THE GROUP CONSISTING OF COPPER, COBALT AND NICKEL, OF A WATER-INSOLUBLE AZO-DYESTUFF HAVING THE FOLLOWING GENERAL FORMULA 